Non-foaming functional fluids



NON-FOAMING FUNCTIONAL FLUIDS Joseph E. Fields, Dayton, Ohio, assignorto Monsanto Chemical Company, St. Louis, Mo., a corporation of DelawareNo Drawing. Application June 7, 1956 Serial No. 589,860

20 Claims. (Cl. 25278) The present invention relates to functionalfluids and more particularly provides non-foaming, functional fluidscomprising an organic phosphate ester base.

Functional fluids containing esters of phosphoric acid have generalutility as force-transmission fluids for the transmission of pressure,power or torque in fluid pres- .sure or torque-activated mechanisms; assynthetic lubri- United States Patent .As examples of phosphate basefunctional fluids may be mentioned the tricresyl phosphate-containingfluids disclosed in U.S. patent application Serial No. 206,128,

phosphate-base lubricant and hydraulic fluids described in the F. J.Watson U.S. Patent Nos. 2,636,861-2, issued April 28, 1953.

While the above-enumerated valuable properties of the phosphate-basefluids adapt them to a great variety of usesin the .mechanical fields,many of such fluids are at a disadvantage in that they often have apronounced tendency to foam under use. Hence, the problem offoam-inhibition is one of major importance to all industries employingthe phosphate-base fluids under foaminducing conditions. The foaming ofthe fluids becomes a particularly great problem when loss of the fluidoccurs by foam seepage whereby proper transmission of force,

flubrication, heat-transfer, etc., are impeded.

Now I have found that the foaming tendency of a functional fluidcontaining at least 45% by weight of a liquid, tribasic, organicphosphate ester is suppressed or .entirely eliminated by "0.0001% to1.0% ofa polymeric alkyl vinyl ether having from 3 to 8 carbon atoms inthe alkyl radical. The

incorporating thereto from presently useful liquid polymeric alkyl vinylethers are further characterized in that 1.0% solutions thereof inbenzene have specific viscosities which range from 0.1 to 1.0 at atemperature of 25 C.

The quantity of the tribasic phosphate present in any particularfunctional fluid is regulated by the use for which the fluid is intended.and the nature of the individual phosphate, as may be apparent to thoseskilled in the art. The present functional fluids may consist entirelyof a liquid organicphosphate, entirely of mixtures .of such phosphatesor they may be mixtures of one or more liquid organic'phosphate's withother fluids known .in the art to be useful as constituents offunctional fluids,

e.g., the known hydraulic fluids, torque converter fluids,heat-transmission fluids, etc. As examples of 2,909,489 Patented Oct.20, 19 5.9

such constituents of the present non-foaming phosphate- ,based fluidsmay be mentioned thepartially chlorinated biphenyls known to the tradeas Aroclors, technical mixtures of biphenyl and terphenyl and otherfluidshaving the property of remaining liquid under a wide range oftemperature conditions and contributing to the utility for which saidfluid is designed. The present functional fluids may also contain smallamounts of agents adapted vto modify the various properties thereof andgenerally known to the trade as additives. Such additives may be minor,but effective, amounts of materials such .as corrosion-inhibitors,anti-rusting agents, detergent additives, extreme pressure-resistingadditives, viscosity index improving agents such as thepolyrneric'higher alkyl methacrylates known 'to the trade as .Acryloids, alkylatedpolystyrenes obtained by alkylating styrene with -olefins having from 6to 12 carbon atoms, etc.

The phosphate which is an essential constituentlof the .presentfunctional fluids may be any normally liquid tribasic ester ofphosphoric acid. Because they are more 'easily available, thehydrocarbon esters are generally preferred. They may be trialky-lphosphates, triaryl phosphates, alkyl diaryl phosphates, aryl dialkylphosphates, tris(alkaryl) or tris(aralkyl) phosphates,alkyl.bis(aralkyl) phosphates, aryl -bis(aralkyl)phosphates, alkyl arylalkaryl phosphates, aralkyl dialkyl phosphates, alkaryl dialkylphosphates, etc. As exemplary of particularly useful phosphates may bementioned:

Trialkyl phosphates in which the alkyl radical has from 4 to 12 carbonatoms, e.g., tributyl phosphates, tri- ,-a1ny1 phosphates, tri-hexylphosphates, trioctyl phosphates, tridecyl phosphates, tridodecylphosphate, and

particularly the branched homologs such as tris(2-ethyl- 'butyl)phosphate, tris(2-methylpentyl) phosphate, tris(2- ethylhexyl)phosphate, and .tris(3,5,5-trimethylhexyl) phosphate.

Triaryl phosphates such as tricresyl phosphate, diphenyl cresylphosphate, liquid mixtures of triphenyl and tricresyl phosphate, etc.

Aryl dialkyl phosphates such as dibutyl phenyl phosphate, amyl phenylphosphate, butyl Z-ethylhexyl phenyl phosphate, butyl octyl cresylphosphate, di(2-ethylhexyl) 'phenyl phosphate, di(6-methylheptyl) cresylphosphate,

dioctyl chlorophenyl phosphate, 2-.ethylhexyl 6-methyl- 'heptyl phenylphosphate, butyl Z-ethylbutyl phenyl phos phate, 2-ethy1hexyl'Z-methylpentyl cresyl phosphate, 11-.

octyl n-hexyl phenyl phosphate, 2-ethylhexyl 2-ethylbutyl phenylphosphate and butyl n-hexyl cresyl phosphate.

Alkyl diaryl phosphates such as 2-ethylhexyl diphenyl phosphate,6-methylheptyl diphenyl phosphate, n-octyl diphenyl phosphate, 2ethylhexyl dicresyl phosphate, 2- ethylhexyl phenyl cresyl phosphate,2-ethy1butyl diphenyl phosphate, 2-methylpentyl dicresyl phosphate,-n-hexyl phenyl cresyl phosphate, nonyl diphenyl and decyl dicresylphosphate.

A specific embodiment of the invention is the provision of non-foamingfunctional fluids consisting essentially of a mixture of a liquid,tribasic phosphate ester and a partially chlorinated diphenylhavingfrom, say, 40% to by weight. of combined chlorine. Such mixturesmay have varying proportions of the phosphate and the biphenylcompound.When designed for use ,as force transmission fluid, however, thephosphate-chlorinated biphenyl mixtures generally contain from 45 to '55parts of the phosphate. ester and from 45 to 55 parts of the chlorinatedbiphenyl. A base stock fluid comprising such a mixture may have added toit from 0.2 to .8 parts by weight of additives compatible therewith andrequired for specific applications.

Another embodiment of the invention of particular interest is theprovision of a non-foaming functional fluid having improved viscosityindex properties. Such a func- .the sphere just touched the bottom ofthe cylinder.

tional fluid may consist essentially of a mixture of the phosphate andthe chlorinated biphenyl together with a small proportion, say, from 0.4to 2 percent by weight of the fluid composition, of an alkylatedpolystyrene as the viscosity index-improving agent.

Still another significant embodiment of the invention is the provisionof non-foaming functional fluids comprising as the base stock, a mixtureof a liquid, tribasic organic phosphate and a partially chlorinatedbiphenyl, to which base stock has been added a small quantity, say, from'1 percent to 5 percent, of a polymeric higher alkyl methacrylatefas aviscosity index improving agent.

The polymeric alkyl vinyl ethers which I have found to possess foamsuppressing properties for functional fluids containing at least 45% byweight of the phosphate esters are viscous liquid to balsam-likeproducts having a 1% Tbenzene specific viscosity of from 0.1 to 1.0 at25 C.

They areobtainable in known manner by heating the monomeric alkyl vinylethers or by contacting them at relatively low temperatures, say, attemperatures of from C. to'100 C., with a catalyst such as iodine,sulfur dioxide or an acidic catalyst, e.g., concentrated mineral acid,aluminum chloride, aluminum sulfate, ferric chlo- I ride, zinc chloride,stannous chloride, etc., as described,

'e.g., by Chalmers in Canadian Journal of Research,

7, 472-80(1932) or in the Reppe US. Patent 2,104,000. Examples ofpresently useful polymers are polymeric isopropyl vinyl ether, isobutylvinyl ether, n-hexyl vinyl ether, Z-ethylhexyl vinyl ether, n-propylvinyl ether, tertamyl vinyl ether, n-octyl vinyl ether, etc., having thespecific viscosity properties herein described. The quantlty of thepolymeric ether which is employed will vary, of course, with the natureof the polymer, the functional fluid and with the use for which it isdesigned; but will be sufiicient to render said fluid substantiallynon-foaming when incorporated therein in a minor amount. Generally, verysmall quantities, say, quantities of from 0.0001

the following examples:

Example 1 The antit'oaming property of a functional fluid may bedetermined according to the procedure generally described in designationL12-445 of the Coordinating Lubricants Research Committee of theCoordinating Research Council, New York. Briefly this procedure involvesbubbling air or an inert gas such as nitrogen through the fluid to betested employing standard apparatus and standard conditions. Thefollowing procedure was employed:

The fluid was placed in a standard l00-ml. graduated cylinderin the topof which was inserted a two-hole rubber stopper. An air-inlet tubeextended through this stopper, to the bottom of which was attached a gasdiff-user or porous stone sphere. The length of the inlet tube wasadjusted so that when the apparatus was assembled, y nitrogen wassupplied at the rate of 0.2 cubic feet per hour, employing a calibratedflowmeter. A cc. test sample was used for each test. 7 a 9 With the airhose disconnected between the flowmeter and the delivery tube to thedilfuser stone, the stone was allowed to soak in the test fluid for 5minutes, at the end of which time the air flow (0.2 cu. ft. per hour)was started through the stone. Zero time was noted when the air ornitrogen bubbles started to rise from the'stone. Readings of the top andbottom foam levels were taken at the end of a 1-minute period. Thevolume of foam was calculated from the two readings. Y The followingfluids were tested:

I. Dibutyl phenyl phosphate '11. 'Octy-l diphenyl phosphate 7 conductingthe test on a larger scale, i.e., using a 1000-ml.

The following antifoam agents were employed with the above fluids at theconcentrations shown in the table below:

(A) A viscous low molecular weight polymeric isobutyl vinyl ether, a 1%benzene solution of the polymer having a specific viscosity of 0.07 at25 C.

'(B) A very viscous higher molecular weight polymeric isobutylvinylether, a 1% benzene solution of the polymer having a viscosity of0.6 at 25 C.

(C) A commercially available, polymeric siloxane antifoaming agent knownto the trade as *DCF 200.

Samples of the respective fluids were mixed respectively with theantifoamants and the resulting mixtures were tested by the testingprocedures described above. The following results were obtained:

Foam (00.) at l-Min. Additive Test Sample in Percent Concentration None.005 .01 .02

I plus 0. I plus B I plus A II II plus 0 II plus A II plus B Example 2In order to test the effect of a viscosity index improver on theantifoaming effect of the polymeric alkenyl alkyl ethers, antifoamingagents were added to dibutyl phenyl phosphate containing 4.0 percent byweight of a polymethacrylate known to the trade as Acryloid V. I.Improver U. The following results were obtained using the testingprocedure of Example 1:

Foam (60.) 1-Min.'Ad-

Example 3 Employing the general procedure of Example 1 but graduateinstead of a 100-ml. graduate and .a 15 0-ml. test sample rather than a25-ml. sample, and employing a 5-minute nitrogen flow period, there wastested the antifoaming effect of the polymeric isobutyl vinyl ethers (A)and (B) of Example 1 on a hydraulic fluid consisting of equal parts byweight of tricresyl phosphate and a chlorinated biphenyl containing 48percent by weight of combined chlorine (herein referred to as basestock) either 1 in the presence or absenceof 0:85 percent by weight ofpolymeric 2-ethy1hexyl acry-late as a viscosity index improving agent.The following results were obtained:

, l M Example 4 a Afunctional fluid was prepared by dissolving one partby weight of an alkylatedpolystyrene madeby all ylating one part by"weight of polystyrene having a molecular weight of about 70,000 withabout 0.5 parts by weight of 'a9 carbo n polyrneric C olefin, into 64parts by weight of chlorinated biphenyl containing 48 percent by weightof combined chlorine; and thereafter, 52 parts by weight of thissolution of the alkylated polystyrene dissolved in the chlorinatedbiphenyl were combined with 48 parts by weight of tricresyl phosphate;Testing of the foam-susceptibility of the fluid conducted as describedin'Exainple 3 gave 750 ml. of foam after 5 minutes. Incorporation of.005 percent by weight of the higher molecular weight polymeric isobutylvinyl ether B of Example 1 into this functional fluid reduced the foamto 70ml, after S'minutes, employing the same te'stingprocedure. 7

:Similarly .good results are obtained by incorporating into thefunctional fluids of Examples l-4, instead of the viscous or veryviscous polymeric isobutyl vinyl ethers, balsarn like polymers ofisobutyl vinyl ether or the balsam-like to viscous liquid polymers ofother alkyl vinyl ethers, e.g., polymeric isopropyl vinyl ether, n-amylvinylether, tert-amyl vinyl ether, n-heptyl vinyl ether or 2eejthylhexylvinyl ether, the specific viscosity of 1% benzene solutions of saidalkyl vinyl ether polymers being from "0.1 to 1.0 at 25 C.

'The present polymeric. alkenyl alkyl ethers suppress or entirelyeliminate the foam susceptibility of other phosphate-base functionalfluids, for example, the following:

(1) The trialkyl phosphates, from tributyl to trilauryl withthepreferred species generally being tri(2-ethylhexyl phosphate. a

(2) The dialkyl monoaryl phosphates wherein the alkyl groupsl'areQ; to C"and the aryl groups are phenyl or cresyl, particularly dibutyl phenylphosphate and di(2- ethylliexyl) phenyl phosphate.

I (3) The monoalkyl diaryl phosphates wherein the alkyl groups are C; toC and the aryl groups are phenyl and/or cresyl, especially Z-ethylhexyldiphenyl phosphate and 6-methylheptyl diphenyl phosphate.

(4) The liquid triaryl phosphates, namely tricresyl phosphate, cresyldiphenyl phosphate and phenyl dicresyl phosphate;

Other. components which may be present together with theliquid phosphateesters are e.g., the partially. chlorinated' biphenylscontaining from,say, 42 percent by Weight to 75 percent by weight of combined chlorine;di-esters of dicarboxylic acids such as dioctyl sebacate and dioctyladipate; and liquid polymeric silicones, all of which components areknown in prior art to be useful in the formulation of functional fluids.

This application is a continuation-in-part of my application, Serial No.370,212, filed July 24, 1953, now abandoned.

What I claim is:

1. A composition consisting essentially of a functional fluid which is aliquid tribasic organic phosphate of the formula O:P(OR) in which each Ris selected from the class consisting of alkyl, aryl, aralkyl andalkaryl radicals and as a defoamant for said fluid from 0.0001% to 1.0%of a viscous liquid to balsam-like polymer of an alkyl vinyl etherhaving from 3 to 8 carbon atoms in the alkyl radical, a 1% benzenesolution of said polymer having a specific viscosity of 0.1 to 1.0 at 25C.

2. A composition consisting essentially of a functional fluid whichis aliquid tribasic organic phosphate of the formula O:P(OR) in which each Ris selected from the class consisting of alkyl, aryl, aralkyl andalkaryl radicals, a viscosity-index improving quantity of a polymericalkyl methacrylate, and as a defoamant for said fluid from 0.0001% to1.0% of a viscous liquid to balsamlike polymer of an alkyl vinyl etherhaving from 3 to 8 carbon atoms in the alkyl radical, a 1% benzenesolution of said polymer having a specific viscosity of 0.1 to 1.0at25C.a

3. A composition consisting essentially of a functional fluid which is amixture consisting of at least 45% by weight of a liquid tribasicorganic phosphate of the formula O=P(OR) 'in which each R is selectedfrom the class consisting of alkyl, aryl, aralkyl and alkaryl radicalswith the balance being a partially chlorinated biphenyl having from 40%to by weight of combined chlorine and as a defoamant for said fluid from0.0001% to 1.0% of a viscous liquid to balsam-like polymer of an alkylvinyl ether having from 3 to 8 carbon atoms in the alkyl radical, a 1%benzene solution of said polymer having a specific viscosity of 0.1 to1.0 at 25 C.

4. A composition consisting essentially of a functional fluid which is amixture consisting of at least 45 'by weight of a liquid tribasicorganic phosphate of the formula O=P(OR) in which each R is selectedfrom the class consisting of alkyl, aryl, aralkyl and alkaryl radicals,with the balance being a partially chlorinated biphenyl having from 40%to 80% by weight of combined chlorine and a viscosity-index improvingquantity of an alkylated polystyrene, and as a defoamant for said fluidfrom 0.0001 to 1.0% of a viscous liquid to balsamlike polymer of analkyl vinylether having from 3 to 8' carbon atoms in the alkyl radical,a 1% benzene solution of said polymer having a specific viscosity of 0.1to 1.0 at 25 C.

5. A composition consisting essentially of a functional fluid which is amixture consisting of at least 45 by weight of a liquid tribasic organicphosphate of the formula O=P(OR) in which each R is selected from theclass consisting of alkyl, aryl, aralkyl and alkaryl radicals, with thebalance being a partially chlorinated biphenyl having from 40% to 80% byweight of combinedchlorine and a'viscosity-index improving quantity of apolymeric alkyl methacrylate, and as a defoamant for said fluid from0.0001% to 1.0% of a viscous liquid tobtlsam-like polymer of an alkylvinyl ether having from 3 to 8 carbon atoms in the alkyl radical, a 1%benzene solution'of said polymer having aspecific viscosity of 0.1 to1.0 at 25 C. t

6. A composition consisting essentially of a functional fluid which is aliquid triaryl phosphate and .as a defoamant for said fluid from 0.0001%to 1.0% of .a viscous liquid to balsam-like polymer of an alkyl vinylether having from 3 to 8 carbon atoms in the alkylradical, 51% benzenesolution of said polymer having a specific viscosity of 0.1 to 1.0 at 25C.

7. A composition consisting essentially of a functional fluid which is.a liquid aryl dialkyl phosphate and as a defoamant for said fluid from0.0001% to 1.0% of a viscous liquid to balsam-like polymer of an alkylvinyl ether having from 3 to 8 carbon atoms in the alkyl radical, a 1%benzene solution of said polymer having a specific viscosity of 0.1 to1.0 at 25 C.

8. A composition consisting essentially of a functional fluid which is aliquid alkyl diaryl phosphate and as a defoarnant for said fluid from0.0001% to 1.0% of a viscous liquid to balsam-like polymer of an alkylvinyl ether having from 3 to 8 carbon atoms in the alkyl radical, a 1%benzene solution of said polymer having a specific viscosity of 0.1 to1.0 at 25 C.

9. A functional fluid consisting essentially of dibutyl phenyl phosphateand as a defoamant for the phosphate from 0.0001% to 1.0% of a viscousliquid to balsam-like polymeric isobutyl vinyl ether, a 1% benzenesolution of said polymeric ether having a specific viscosity of 0.1 to1.0 at 25 C.

10. A composition consisting essentially of a functional fluid which isa mixture consisting of at least 45% by Weight of a tricresyl phosphatewith the balance being a partially chlorinated biphenyl having from 40%to 80% by weight of combined chlorine and as a defoamant for said fluidfrom 0.0001% to 1.0% of a viscous liquid to balsam-like polymericisobutyl vinyl ether, a 1% benzene solution of said polymeric etherhaving a specific viscosity of 0.1 to 1.0 at 25 C.

11. A functional fluid consisting essentially of octyl diphenylphosphate and as a defoarnant for said phosphate from 0.0001% to 1.0% ofa viscous liquid to balsam-like polymeric isobutyl vinyl ether, a 1%benzene solution of said polymeric ether having a specific viscosity of0.1 to 1.0 at 25 C.

12. A composition consisting essentially of a functional fluid which isa mixture of dibutyl phenyl phosphate and a viscosity-index improvingquantity of a polymeric alkyl methacrylate and as a defoamant for saidfluid from 0.0001% to 1.0% of a viscous liquid to balsam-like polymericisobutyl vinyl ether, a 1% benzene solution of said polymeric etherhaving a specific viscosity of 0.1 to 1.0 at 25 C.

13. A composition consisting essentially of a functional fluid which isa mixture containing at least 45% by weight of tricresyl phosphate withthe balance being partially chlorinated biphenyl having from 40% to 80%by weight of combined chlorine and an alkylated polystyrene in aviscosity-index improving quantity, said composition containing as a'defoamant for said fluid from 0.0001% to 1.0% of a viscous liquid tobalsam-like polymen'c isobutyl vinyl ether, a 1% benzene solution ofsaidpolymeric ether having a specific viscosity of 0.1 to 1.0 at 25 C.

14. The method of suppressing the foaming tendency of a functional fluidconsisting essentially of a liquid tribasic organic phosphate of theformula O=P(OR) in which each R is selected from the class consisting ofalkyl, aryl, aralkyl and alkaryl radicals which comprises adding to saidfluid from 0.0001% to 1.0% of a viscous liquid to balsam-like polymer ofan alkyl vinyl ether having from 3 to 8 carbon atoms in the alkylradical, a 1% benzene solution of said polymer having a specificviscosity of 0.1 to 1.0 at 25 C.

15. The method of suppressing the foaming tendency of a functional fluidconsisting essentially of a liquid triaryl phosphate, \which comprisesadding to said fluid from 0.0001% to 1.0% of a viscous liquid tobalsam-like polymer of an alkyl vinyl ether having from 3 to 8 carbonatoms in the alkyl radical, a 1% benzene solution of said polymer havinga specific viscosity of 0.1 to 1.0 at 25 C.

16. The method of suppressing the foaming tendency of a functional fluidconsisting essentially of a liquid diaryl alkyl phosphate, whichcomprises adding to said fluid from 0.0001% to 1.0% of a viscous liquidto balsamlike polymer of an alkyl vinyl ether having from 3 to 8 carbonatoms in the alkyl radical, a 1% benzene solution of said polymer havinga specific viscosity of 0.1 to 1.0 at 25 C. I

17. The method of suppressing the foaming tendency of a functional fluidconsisting essentially of a liquid aryl dialkyl phosphate, whichcomprises adding to said fluid from 0.0001% to 1.0% of a viscous liquidto balsamlike polymer of an alkyl vinyl ether having from 3 to 8 carbonatoms in the alkyl radical, a 1% benzene solution of said polymer havinga specific viscosity of 0.1 to 1.0 at 25 C.

18. The method of suppressing the foaming tendency of a functional fluidconsisting essentially of a mixture consisting ofat least 45 by weightof a liquid tribasic organic phosphate of the formula O=P(OR) in whicheach R is selected from the class consisting of alkyl, aryl, aralkyl andalkaryl radicals with the balance being a partially chlorinated biphenylhaving from 40% to by weight of combined chlorine, which comprisesadding to said fluid from 0.0001% to 1.0% of a viscous liquid tobalsam-like polymer of an alkyl vinyl ether having from 3 to 8 carbonatoms in the alkyl radical, a 1% benzene solution of said polymer havinga specific viscosity of 0.1 to 1.0 at 25 C.

19. The method of suppressing the foaming tendency of a functional fluidconsisting essentially of dibutyl phenyl phosphate, which comprisesadding to said fluid from 0.0001% to 1.0% of a viscous liquid tobalsamlike polymeric isobutyl vinyl ether, a 1% benzene solution of saidpolymer having a specific viscosity of 0.1 to 1.0 at 25 C.

20. The method of suppressing the foaming tendency of a functional fluidconsisting essentially of a mixture consisting of at least 45 by weightof tricresyl phosphate with the balance being a partially chlorinatedbiphenyl having from 40% to 80% by weight of combined chlorine, whichcomprises adding to said fluid from 0.0001% to 1.0% of a viscous liquidto balsam-like polymer of an alkyl vinyl ether having from 3 to 8 carbonatoms in theralkyl radical, a 1% benzene solution of said polymer havinga specific viscosity of 0.1 to 1.0 at 25 C.

References Cited in the file of this patent UNITED STATES PATENTS2,430,858 Borsolf et al. Nov. 18, 1947' 2,469,285 White May 3, 19492,575,298 Ryznar Nov. 13, 1951 2,695,892v Jaccard et al. Nov. 30, 19542,707,176 Gamrath et al. Apr. 26, 1955 FOREIGN PATENTS 7 64,456Netherlands Oct. 15, 1949

1. A COMPOSITION CONSISTING ESSENTIALLY FO A FUNCTIONAL FLUID WHICH IS A LIQUID TRIBASIC ORGANIC PHOSPHATE OF THE FORMULA0=P(OR)3 IN WHICH EACH R IS SELECTED FROM THE CLASS CONSISTING OF ALKYL, ARYL, ARALKYL AND ALKARYL RADICALS AND AS A FEFOAMANT FOR SAID FLUID FROM 0.0001% TO 1.0% OF A VISCOUS LIQUID TO BALSAM-LIME POLYMER OF AN ALKYL VINYL ETHER HAVING FROM 3 TO 8 CARBON ATOMS IN THE ALKYL RADICAL, A 1% BENZENE SOLUTIONOF SAID POLYMER HAVING ASPECIFIC SISCOSITUY OF 0.1 TO 1.0 AT 25*C. 